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ACID BASE

PART
01
Operational Definition
• ACIDS (acidus: “sour or tart) • BASES (“to bring low”)
– Turns litmus paper red – Turns litmus paper blue
– React with active metal by – Feel slippery or soapy on the
dissolving metals producing H2 skin
– Corrosive to skin – Tastes bitter
– Taste sour (when diluted – Reacts with acids to form water
enough to be safely tasted) & salt
– React with bases/alkalis to
form water & salt
CONCEPTUAL DEFINITION

• Arrhenius Theory – Formulated by Swedish physical


chemist Svante Arrhenius
• Bronsted-Lowry Theory – Formulated by Danish
chemist Johannes Nicolaus Bronsted & British chemist
Thomas Lowry
• Lewis Theory – Formulated by American chemist
Gilbert Lewis
S. Arrhenius J.N. Brønsted T. Lowry G.N. Lewis
Arrhenius Theory
• Arrhenius acid – Substances upon dissociation in
water gives an H+

• Arrhenius base – Substances upon dissociation in


water gives an OH-
+
H in water

◆H3O+ - hydronium ion


—Used interchangeably with H+
The role of water as a solvent in ionic
substances are important to Arrhenius
acid-base behavior.
Its major weakness is it failed to
recognize that acid-base reactions can
occur in the gas phase & in nonionizable
solvents.
HCl in Water
HCl in Water

◆Proton-Transfer Reaction
Bronsted- LowryTheory
•Bronsted-Lowry acid – Substances that donates a
proton (H+/H3O+) to other substances

• Bronsted-Lowy base – Substances that accepts a


proton from any other substances
Bronsted- LowryTheory
–Any molecular or ionic compound that can
accept a proton whether in solution or in gas
solvent.

• Conjugate acid-base pair – An acid & a base


that are related by a transfer of proton
Conjugate Acid-Base Pair

• HNO2(aq) + H2O(l) ↔ NO2-(aq) + H3O+(aq)

• NH3(aq) + H2O(l) ↔ NH4+(aq) + OH-(aq)


(i) The protonic definition cannot be used to explain the reactions
occuring in non-protonic solvents such as SO2, N2O4, etc.

(ii) It cannot explain the reactions between acidic oxides like etc
and the basic oxides like etc which take place even in the absence of
the solvent e.g.,

CaO + SO3 → SO4


There is no proton transfer in the above example.

(iii) Substances like BF3, AlCl3 etc, do not have any hydrogen and
hence cannot give a proton but are known to behave as acids.
Lewis Theory
• Lewis acid – Substances that accepts a lone-pair (pair of
electron) from another molecule in completing the octet

• Lewis base – Substances which has a lone pair of


electrons that can be donated to complete the octet of
another atom.
Lewis Theory
• The fundamental acid-base reaction in the Lewis
concept is the formation of a coordinated covalent bond
between an acid & a base. The process called
neutralization or simple coordination. The product is a
coordinated compound or coordination complex.
Summary
Theory Acid Definition Base Definition

Arrhenius Releases H+ ion Releases OH- ion

Brønsted-Lowry Proton donor Proton acceptor

e- pair/lone pair
Lewis e- pair/lone pair donor
acceptor
 Compounds that have one more proton to give
– Example:
diprotic = H2SO4, triprotic = H3PO4

These acids like water & other special compounds have


conjugates which are amphoteric
Is the capacity of a compound to act as an acid or as a base
Example: Water
2H2O(l) ↔ H3O+(aq) + OH-(aq)

Another example: HSO4-


HSO4-(aq) ↔ SO42-(aq) + H3O+(aq)
1) Identify what type of 2) Give the conjugate
acid/base
Practice are the ff:
Exercise base of HClO4, H2S,
a) NaOH PH4+, HCO3- , H2PO4?
b) HCl 3) Give the conjugate
c) NH3 acid of CN-, SO42-, H2O,
d) HNO2 HCO3- , HSO4?
e) H2O
f) BF3
STRENGTH OF ACIDS & BASES

 Why are some acid/base strong & other weak?


– Depends on its ability to donate/accept proton.

The stronger an acid, the weaker its conjugate


base; the stronger the base, the weaker its
conjugate acid.
STRENGTH OF ACIDS & BASES
 Strong acid – Completely transfers its protons to
water, leaving no undissociated molecules in solution.
– Conjugate base: negligible
 Weak acid – Partially dissociates in aqueous soln &
therefore exist as a mixture of acid molecule & their
constitutent ions.
– Conjugate base: weak
STRENGTH OF ACIDS & BASES

 Strong acids (7 most common):


– Monoprotic: HCl, HBr, HI, HNO3, HClO3, HClO4
– Diprotic H2SO4

 Strong Base – All hydroxides of alkali metals (Grp 1A)


& akaline earth metals (Grp 2A)
STRENGTH OF ACIDS & BASES
TYPES OF ACIDS
• Binary acids
– Acids with only 1 element aside from H+

• Oxyacids (oxoacids)
– Acids with oxyanion/oxoanion (ions paired with oxygen)

• Carboxylic acids
– Acids that contain carboxyl groups (-COOH)
Binary Acid
◆Acids containing anions whose names end in -ide
are named by changing the –ide ending to -ic,
adding the prefix hydro- to this anion name, and
then following with the word acid
Anion Corresponding Acid

Cl- (chloride) HCl (hydrochloric acid)

S2- (sulfide) H2S (hydrosulfuric acid)


Oxyacids
◆Acids containing anions whose names end in -ate or -
ite are named by changing –ate to -ic and -ite to -ous
and then adding the word acid. Prefixes in the anion
name are retained in the name of the acid:
Anion Corresponding Acid
ClO4- (perchlorate) HClO4 (perchloric acid)

ClO3- (chlorate) HClO3 (chloric acid)


ClO2- (chlorite) HClO2 (chlorous acid)
ClO- (hypochlorite) HClO (hypochlorous acid)
Oxyacids
Common ions ending in -ate

AsO43- NO3- SiO32- AsO43- ClO3-

BO3- PO43- SO42- IO4- CrO42-


TYPES OF WEAK BASE
2 categories:
– Neutral substances that have an atom with a
nonbonding pair of electron that can serve as a proton
acceptor
Most contains N atom: ammonia (NH3) & amines
(RNH2)
– Anions of weak acid
• Example: HClO (weak acid) = ClO- (conj. base = weak)
Factors that affect Acid strength

Essentially nonpolar H-X bond produce neither acid nor basic


aqeous soln.
2) H – X bond strength
Very strong bonds are less easily dissociated than weaker ones
3) Stability of conjugate base, X-
The greater the stability of the conjugate base, the stronger
the acid
Relative Acid Strength

Binary Acid
– Group (H – X bond strength) : bond strength
decreases, acidity increases down a group
HCl > HF; H2S > H2O
– Row (H – X bond polarity): bond polarity
increases, acidity increases from left to right
CH4 < NH3 << H2O < HF
Relative Acid Strength
Relative Acid Strength
Oxyacid (oxoacid)
– Acids in which OH groups & possibly
additional oxygen atoms are bound to a
central atom
Y: metal (base)
Y: nonmetal (acid)
Relative Acid Strength
Oxyacid (oxoacid)
—Same # of O atoms, different Y
• Acidity increases as EN of Y increases
• HIO (EN = 2.5) < HBrO (EN = 2.8) < HClO (EN =
3.0)
—Same central atom Y, different # of O atoms
• Acidity increases as # of O attached to Y
increases
• HClO < HClO2 < HClO3 < HClO4
Relative Acid Strength
Carboxylic Acid
—Presence of electron withdrawing group (O, Cl,
N)
• Increases polarity; increases acidity
—Presence of electron donating group (C groups)
• Stabilizes the substance; decreases acidity
Carboxylic Acid
a. H2SeO4
b. KOH
c. (CH3)2CHCOOH
d. (CH3)2CHNH2
• Arrange the compounds in each of the ff series in
order of increasing acid strength:
1. AsH3, HI, NaH, H2O
2. H2SO4, H2SeO3, H2SeO4
3. Formic acid (HCOOH), chloroacetic acid
(CH2ClCOOH), acetic acid (CH3COOH)
PART
02
pH
Acid-Base Property of Water

 Water –unique solvent; amphoteric; weak


electrolyte; ionizes to a small extent
Acid-Base Property of Water
 Kc = [H3 + -
O ][OH ] = + -
[H ][OH ] =1.00×10-14

(@ 25°C)=KW
Kw – ion-product constant of water
—Neutral: [H+] = [OH-] = 1.00×10-7 M
—Acidic: [H ] > [OH ]
+ -

—Basic: [H+] < [OH-]


pH Scale
◆Proposed by Danish biochemist Søren Peter Lauritz Sørensen
—pH = -log[H+] = -log [H3O+]
—[H+] = antilog(-pH) = 10-pH
◆From autoionization of water: pH + pOH = 14.00
pH Scale
EExamples

1) Calculate the pH 1) Calculate the pH


a) [HCl] = 5.6×10-6 M a) 0.040 M HClO4
b) [KOH] = 1.9×10-6 M b) 0.028 M NaOH
+ - c)0.0011 M Ca(OH)2
2) Calculate [H ] & [OH ]
d)6.50 x 10-3 M KOH
a) pH = 9.18
b) pOH = 3.00
1. What is the concentration of nitric acid if its pH is
2.34? Its [OH-]?

2. A solution with a H+ concentration of 1.00 x 10-7 M


is said to be neutral. Why?
Ionization Constant (Weak Acids)
Ionization Constant (Weak Bases)
Relationship of Ka & Kb

•Qualitative
—Stronger acid have weaker conjugate
base
•Quantitative
—Ka×Kb = KW
Examples
1)Calculate the pH & % ionization:
a. 0.20 M HCN (Ka=4.9×10-10)
b.0.15 M NH3 (Kb = 1.8×10-5)

2) Calculate Ka & Kb
a. 0.10 M formic acid with pH = 2.38
b.0.035 M ephedrine (C10H15ON) with a pH = 11.33
Practice niacin

1)Calculate the pH & % ionization:


a. 0.010 M niacin (Ka = 1.5×10-5)
b. 0.20 M pyridine (Kb = 1.7×10-9)
pyridine
2) Calculate Ka & Kb
a. 0.020 M niacin with pH = 3.26
b.5.0×10-3 M codeine (C18H21NO3) with pH = 9.94
PART
03
Neutralization
& Salts
Neutralization

Process where an acid reacts with a base to form


salt and water.

ACID + BASE → SALT + WATER


HCl + NaOH → NaCl + H2O
Neutralization
Acid + Base → Salt + Water (double
replacement)
• HCl(aq) + NaOH (aq) → HOH(l) + NaCl(aq)

• H2SO4(aq) + 2KOH(aq) → 2HOH(l) + K2SO4(aq)


Neutralization
Example:
• HNO3(aq) + Ca(OH)2(aq) →
• H3PO4(aq) + Mg(OH)2(aq) →

• HBr (aq) + LiOH (aq) →


• H2CrO4 (aq) + NaOH (aq) →
Salts
• Salt formed by neutralization rxn depends on the
acid & alkali/base used.
• The salt contains the cation of the base and anion
of the acid molecule
• Salts of sulfuric acid are called sulfates
• Salts of hydrochloric acid are called chlorides
• salts of nitric acid are called nitrates
Are salts acidic? Basic? Or neutral?
Acid-Base Properties of Salt
• Assume that when salts dissolve in water, are
completely ionized.
• Nearly all salts are strong electrolyte.
• Acid-base property: due to the behavior of their
cations & anions

• Hydrolysis — Rxn of ions with H2O to form H+(aq) or


OH-(aq)
Acid-Base Properties of Salt
• Anions
—from WEAK ACIDS react with water to form
OH- ions & are thus BASIC
—from STRONG ACIDS do not influence pH
—that have IONIZABLE PROTONS are
AMPHOTERIC; behavior are determined by
relative magnitude of Ka & Kb
Acid-Base Properties of Salt
• Cations:
—that’re CONJ. ACID OF WEAK BASES react w/
water to form H+ ions & are thus ACIDIC
—that’re SMALL, HIGHLY CHARGED AND
METALLIC react w/ H2O to decrease the pH of
the soln & are thus ACIDIC
—ALL OTHERS do not influence pH
Acid-Base Properties of Salt
Qualitative Prediction of pH of a Soln of Salt
1) Salts derived from SB & SA
—cation(B+) & anion(A-) do not hydrolyze; pH=7
2) Salts derived from SB & WA
—A-: SCB, B+: do not hydrolyze; pH > 7 (BASIC)
3) Salts derived from WB & SA
—B+: SCA, A-: do not hydrolyze; pH < 7 (ACIDIC)
4) Salts derived from WB & WA
—B+ & A- :Both hydrolyzes; depends on Ka & Kb
—if Ka > Kb ⇒ acidic; Ka < Kb = basic
Exercise: Identify whether acidic, basic or neutral
• Example:
◆ Practice:
1) NaCl 1) Ca(NO3)2
2) NaClO 2) Ba(C2H3O2)2
3) NH4Cl 3) Al(NO3)3
4) NH4CN 4) (NH4)2CO3
5) KNO3
5) NH4C2H3O2
-Ka of HCO3- = 5.6 x 10-11
-Ka of HCN = 6.2 x 10-10
–Kb of NH3 = 1.8 x 10-5
–Ka of HAc = 1.8 x 10-5
Titration

Experimental process of reacting


a solution of unknown
concentration with one of known
concentration (standard solution)
• ASE
Example:
Suppose we have an HCl soln of an unknown conc
& NaOH soln that we know to be 0.100 M. To
determine the conc of HCl, we take specific
volume of that soln, say 20.00mL. We then slowly
add the standard NaOH soln to it until the
neutralization reaction between the HCl & NaOH
is complete.
@ neutralization: moleACID = moleBASE
pH Titration Curve
• pH profile of a SA-SB titration
pH Titration Curve
Acid-Base Titration
• Equivalence point/endpoint
—The point at which stoichiometrically equivalent
quantities are brought together
—@ neutralization: moleACID = moleBASE
—@ equivalence point: moleACID = moleBASE

• The shape of pH titration curve makes it possible to


determine the equivalence point of titration.
—Can also be used to determine Ka of weak acid & Kb of
weak base being titrated
Acid-Base Indicators
• An indicator is a large organic molecule that
works somewhat like a "color dye."
• They change color depending whether the
solution is acidic or basic
• Used to determine the equivalence point of
titration.
Common Acid-Base Indicators
Indicator Approximate pH range for Color Change
Color Change (from acidic to basic)

methyl red 4.2 — 6.0 Red to yellow

bromothymol blue 6.0 — 7.6 Yellow to blue

phenolpthalein 8.2 — 10 Colorless to pink

litmus 5.5 — 8.2 Red to blue

Bromocresol green 3.8 — 5.4 Yellow to blue

thymol blue 8.0 — 9.6 Yellow to blue

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